CN101245155A - Pyrrolyl modification complex function polymeric adsorbent and manufacture method thereof - Google Patents
Pyrrolyl modification complex function polymeric adsorbent and manufacture method thereof Download PDFInfo
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- CN101245155A CN101245155A CNA2008100244354A CN200810024435A CN101245155A CN 101245155 A CN101245155 A CN 101245155A CN A2008100244354 A CNA2008100244354 A CN A2008100244354A CN 200810024435 A CN200810024435 A CN 200810024435A CN 101245155 A CN101245155 A CN 101245155A
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 42
- 230000004048 modification Effects 0.000 title claims description 26
- 238000012986 modification Methods 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title description 10
- 125000000168 pyrrolyl group Chemical group 0.000 title description 6
- 238000000034 method Methods 0.000 title description 2
- 229920005989 resin Polymers 0.000 claims abstract description 69
- 239000011347 resin Substances 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 230000008961 swelling Effects 0.000 claims abstract description 21
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000013557 residual solvent Substances 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 33
- 239000000460 chlorine Substances 0.000 claims description 33
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 20
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 12
- 150000003233 pyrroles Chemical class 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- HCUARRIEZVDMPT-UHFFFAOYSA-N Indole-2-carboxylic acid Chemical compound C1=CC=C2NC(C(=O)O)=CC2=C1 HCUARRIEZVDMPT-UHFFFAOYSA-N 0.000 claims description 11
- 235000005074 zinc chloride Nutrition 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000007306 functionalization reaction Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 6
- OLNJUISKUQQNIM-UHFFFAOYSA-N indole-3-carbaldehyde Chemical compound C1=CC=C2C(C=O)=CNC2=C1 OLNJUISKUQQNIM-UHFFFAOYSA-N 0.000 claims description 6
- -1 substituted-nitrobenzene Chemical class 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- GVSMQKKMAYLKMM-UHFFFAOYSA-N 3-chloro-1h-indole Chemical class C1=CC=C2C(Cl)=CNC2=C1 GVSMQKKMAYLKMM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002475 indoles Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 5
- 238000005342 ion exchange Methods 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000009977 dual effect Effects 0.000 abstract description 3
- 239000010413 mother solution Substances 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000011324 bead Substances 0.000 abstract 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 abstract 1
- 102000004169 proteins and genes Human genes 0.000 abstract 1
- 108090000623 proteins and genes Proteins 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 238000004132 cross linking Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 230000002459 sustained effect Effects 0.000 description 18
- 238000005406 washing Methods 0.000 description 14
- 229920005990 polystyrene resin Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 241001566735 Archon Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000007265 chloromethylation reaction Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 230000037396 body weight Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a pyrryl modified bi-functional polymeric adsorbent with the structural unit shown in the drawing, wherein R is shown in the drawing. The specific surface area of the bi-functional polymeric adsorbent is 50 to 1600 m<2>/g, the pore volume is 0.01-1.0 cm<3>/g, and the exchange capacity is 0.1-5.0 mmol/g. The preparation method for the resin is that chloromethylated beads are swelled in solvents such as nitrobenzene, etc. to add catalyst to obtain polystyrene-divinyl benzene adsorbent; reaction mother solution is exhausted and residual solvent and catalyst are washed away; swelling is carried out by adding in the functionalized pyrryl agent, so as to further react with the residual chloromethyl on the internal and external surfaces of the resin to obtain the pyrryl modified bi-functional polymeric adsorbent. The resin has dual functions of absorbing and ion exchanging (coordination). The resin also has hydrophilic property, alkali pyrryl functional groups and hydrophobic styrene frame and has excellent affinity for amphoteric bioreagents such as protein; and the acid-base interaction between the pyrryl functional groups and acid organic materials is particularly in favor of the separation of acid organic materials.
Description
Technical field
The present invention relates to a kind of pyrryl modification complex function polymeric adsorbent and preparation method thereof.
Background technology
In recent years, the complex function polystyrene resin is owing to have characteristics such as high-specific surface area, various surface chemistry, high mechanical strength, increasingly extensive water body purification, extract drugs, the chromatographic separation technology field of being applied to.Calendar year 2001, Nanjing University applied for " a kind of synthetic method with superhigh cross-linking weak basic anion exchange resin of dual-use function " patent (ZL0134143.2), its key step is: a) utilize whiteruss, the 200# solvent oil is made pore-creating agent, use magnesiumcarbonate, gelatin, one or more mixtures such as polyvinyl alcohol are made dispersion agent, vinylbenzene is made monomer, divinylbenzene is made linking agent, peroxidation benzene first phthalein is made initiator, adopt suspension polymerization, synthetic low crosslinking degree macroporous polystyrene, select steam distillation for use or use acetone according to pore-creating agent character then, lower boiling gasoline extracting pore-creating agent, air stream drying gets the low cross-linking macropore polystyrene resin (ps) again, following abbreviation Archon pearl body; B) soak Archon pearl body with Archon pearl body weight 4-7 chloromethyl ether doubly, zinc chloride with Archon pearl body weight 30-50% is made catalyzer, carry out chloromethylation at 36-42 ℃, reach more than 18% until cl content, take out most chlorination mother solution, water or organic solvent are washed remaining chlorination mother solution in the most resin, and be dry then, get dry chloroethyl crosslinked polystyrene, following abbreviation chlorine ball; C) at chloromethylation low cross-linking polystyrene in cross-linking process after one's death, make solvent with oil of mirbane or substituted-nitrobenzene etc., with Louis's acid as catalyst such as zinc chloride, iron trichloride, tin tetrachloride, consumption is the 5-30% of chlorine ball weight, be warming up to suitable temp, determine reaction end by control resin residual chlorine content; D) after the reaction, take out most reaction mother liquor, with one or more organic solvent washing polymeric adsorbents in ethanol, methylal, acetone, the methyl alcohol, directly use the dimethylamine amination then, the dimethylamine consumption is 1-3 a times of chlorine ball, can make the superhigh cross-linking weak basic anion exchange resin of a series of different specific surface areas, different exchange capacities.This patent has related to employing dimethylamine modification polymeric adsorbent and has obtained the composite function super high crosslinked resin of amine-modified weak base in the resin synthesis step, but does not mention the functional group resin surface grafting pyrroles.Literature search shows that complex function adsorption resin that pyrryl is modified and preparation method thereof is not seen bibliographical information.
Summary of the invention
1. invent the technical problem that will solve
The purpose of this invention is to provide a kind of pyrryl modification complex function polymeric adsorbent and preparation method thereof.Resin of the present invention has both wetting ability, lipophilicity and weakly alkaline, overcome general polymeric adsorbent and can only can only have the dual function of absorption and ion-exchange by the shortcoming of ion-exchange (coordination) effect fractionation by adsorption hydrophilic organics hydrophilicity by hydrophobic interaction fractionation by adsorption lipophilicity organism and common basic resin.
2. technical scheme of the present invention is as follows:
A kind of pyrryl modification complex function polymeric adsorbent, its structural unit is as follows:
Wherein R is:
Can find out from structural unit that the existing alkalescence of this resin, wetting ability functionalization pyrrole group (comprise pyrrole group, N-methylpyrrole group, N-N-ethyl pyrrole N-group, benzopyrrole (indoles) group, 3-chloro indolyl radical, indoles-3-sulfonic acid group, indole-2-carboxylic acid group, indole-3-formaldehyde group etc.), hydrophobicity vinylbenzene skeleton is arranged again.This resin can be by the functionalization pyrrole group nitrogen-atoms and positively charged ion or the organism with sky electronic orbit carry out ion exchange (or coordination), carry out hydrophobic absorption and micropore filling effect between hydrophobicity that also can be by the skeleton of resin own and the organic hydrophobic part.
Described a kind of pyrryl modification complex function polymeric adsorbent, its specific surface area is 50-1600m
2/ g, micro pore volume are 0.01-1.0cm
3/ g, exchange capacity are 0.1-5.0mmol/g.
A kind of preparation method of pyrryl modification complex function polymeric adsorbent may further comprise the steps:
A) chlorine ball (chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resin) is swollen in oil of mirbane, substituted-nitrobenzene, ethylene dichloride or the orthodichlorobenzene solvent, add zinc chloride or iron trichloride, tin tetrachloride as catalyzer, progressively be warming up to 20-120 ℃, control resin residual chlorine content is that 4-15% determines reaction end, obtains the polystyrene-divinylbenzene polymeric adsorbent of different degree of crosslinking;
B) steps A) after the reaction, take out most reaction mother liquor, residual solvent and the catalyzer of one or more organic solvent flush awaies in water or ethanol, acetone, methylal, the methyl alcohol; Make swelling agent with trichloroethane, oil of mirbane, substituted-nitrobenzene, ethylene dichloride, orthodichlorobenzene, benzene or toluene then, consumption is 2-6 a times of weight resin; Under 30-90 ℃ temperature, add functionalization pyrroles reagent, consumption is 0.5-3 a times of weight resin, further react with resin surfaces externally and internally residual chlorine methyl, reaction times is 2-24 hour, can make the pyrryl modification complex function polymeric adsorbent of serial different specific surface area, different exchange capacities.
The preparation method of above-mentioned a kind of pyrryl modification complex function polymeric adsorbent, steps A) in, the consumption of oil of mirbane, ethylene dichloride or orthodichlorobenzene is 2-6 a times of chlorine ball; In the crosslinking reaction process, the amount of catalyzer zinc chloride, iron trichloride or tin tetrachloride is the 4-50% of chlorine ball weight behind the chlorine ball.
The preparation method of above-mentioned a kind of pyrryl modification complex function polymeric adsorbent, step B) in, the functional group R of functionalization pyrroles's reagent can be the pyrroles, the N-methylpyrrole, the N-N-ethyl pyrrole N-, indoles, 3-chloro indoles, indoles-3-sulfonic acid, indole-2-carboxylic acid, indole-3-formaldehyde.
The preparation method of described a kind of pyrryl modification complex function polymeric adsorbent, normally, under the identical situation of other conditions, functionalization pyrroles's reagent dosage is many more, reaction times is long more, temperature of reaction is high more, and the specific surface area of prepared complex function adsorption resin is low more, and loading capacity is high more.
3. beneficial effect
The invention discloses a kind of pyrryl modification complex function polymeric adsorbent and preparation method thereof, this resin has the dual function of absorption and ion-exchange (coordination).The present invention adopts the functionalization pyrroles to modify to obtain contains the pyrryl complex function adsorption resin, in its adsorption mechanism in the pyrryl of band lone-pair electron the static and the coordination of nitrogen-atoms remarkable, and because pyrrole ring can form big delocalized bond with adsorbate, its thermostability also is improved to some extent than general amido modified resins.It possesses wetting ability, alkaline pyrroles's functional group and hydrophobicity vinylbenzene skeleton simultaneously, and both sexes biological reagents such as albumen are had good affinity; And pyrroles's functional group and acid organism have acid-base function, is particularly conducive to acid organic separation.Therefore, fields such as the improvement of this resin organic concentration and separation, deep desulfurization of fuel oil and organic industrial sewage in medicine separation, food decolouring, albumen purification, aqueous systems and resource utilization have broad application prospects.
Embodiment
Further specify the present invention by the following examples.
Embodiment 1
Get the 30g degree of crosslinking and be 8% chlorine ball productions such as (, cl content is 18%) Langfang, Hebei electric power resin processing plants, add oil of mirbane swelling 12h in the 250ml there-necked flask of 60ml; Speed with 1 ℃/2min is warming up to 80 ℃, adds the zinc chloride of 2g under the stirring velocity of-Ding, and sustained reaction to resin residual chlorine content is 12%, obtains the polystyrene-divinylbenzene polymeric adsorbent; Take out most reaction mother liquor, with 600ml methylal and the above-mentioned polystyrene resin of methanol wash.The orthodichlorobenzene swelling 12h that adds 60ml; The control solution temperature is 40 ℃, under the stirring velocity of 110rpm, constantly drip pyrroles 80ml sustained reaction 8h, take out and filter, with weight percent 4% hydrochloric acid drip washing, extracting, oven dry, products therefrom is the pyrryl modification complex function polymeric adsorbent, this resin pyrryl content (exchange capacity) is 3.2mmol/g, and micro pore volume is 0.17cm
3/ g, specific surface area is 470m
2/ g.The resin structure unit is as follows:
Embodiment 2
Get the 30g degree of crosslinking and be 8% chlorine ball productions such as (, cl content is 18%) Langfang, Hebei electric power resin processing plants, add oil of mirbane swelling 12h in the 250ml there-necked flask of 60ml; Speed with 1 ℃/2min is warming up to 80 ℃, adds the zinc chloride of 2g under certain stirring velocity, and sustained reaction to resin residual chlorine content is 15%, obtains the polystyrene-divinylbenzene polymeric adsorbent; Take out most reaction mother liquor, with 600ml methylal and the above-mentioned polystyrene resin of methanol wash.The orthodichlorobenzene swelling 12h that adds 60ml; The control solution temperature is 40 ℃, under the stirring velocity of 110rpm, constantly drip pyrroles 10ml sustained reaction 8h, take out and filter, with weight percent 4% hydrochloric acid drip washing, extracting, oven dry, products therefrom is the pyrryl modification complex function polymeric adsorbent, this resin pyrryl content is 0.9mmol/g, and micro pore volume is 0.04cm
3/ g, specific surface area is 65m
2/ g.The resin structure unit is as follows:
Embodiment 3
Get the 30g degree of crosslinking and be 8% chlorine ball productions such as (, cl content is 18%) Langfang, Hebei electric power resin processing plants, add oil of mirbane swelling 12h in the 250ml there-necked flask of 60ml; Speed with 1 ℃/2min is warming up to 80 ℃, adds the zinc chloride of 2g under certain stirring velocity, and sustained reaction to resin residual chlorine content is 12%, obtains the polystyrene-divinylbenzene polymeric adsorbent; Take out most reaction mother liquor, with 600ml methylal and the above-mentioned polystyrene resin of methanol wash.The oil of mirbane swelling 12h that adds 60ml; The control solution temperature is 40 ℃, under the stirring velocity of 110rpm, constantly drip N-methylpyrrole 80ml sustained reaction 8h, take out and filter, with weight percent 4% hydrochloric acid drip washing, extracting, oven dry, products therefrom is a N-methylpyrrole base modified composite function absorption resin, this resin N-methylpyrrole base content is 4.2mmol/g, and micro pore volume is 0.20cm
3/ g, specific surface area is 220m
2/ g.The resin structure unit is as follows:
Embodiment 4
Get the 30g degree of crosslinking and be 8% chlorine ball productions such as (, cl content is 18%) Langfang, Hebei electric power resin processing plants, add oil of mirbane swelling 12h in the 250ml there-necked flask of 60ml; Speed with 1 ℃/2min is warming up to 80 ℃, adds the zinc chloride of 2g under certain stirring velocity, and sustained reaction to resin residual chlorine content is 8%, obtains polystyrene resin; Take out most reaction mother liquor, with 600ml methylal and methanol wash polystyrene resin.The oil of mirbane swelling 12h that adds 60ml; The control solution temperature is 40 ℃, under the stirring velocity of 110rpm, constantly drip N-N-ethyl pyrrole N-80ml sustained reaction 8h, take out and filter, with weight percent 4% hydrochloric acid drip washing, extracting, oven dry, products therefrom is a N-N-ethyl pyrrole N-base modified composite function absorption resin, this resin N-N-ethyl pyrrole N-base content is 2.1mmol/g, and micro pore volume is 0.55cm
3/ g, specific surface area is 810m
2/ g.The resin structure unit is as follows:
Embodiment 5
Get the 30g degree of crosslinking and be 8% chlorine ball productions such as (, cl content is 18%) Langfang, Hebei electric power resin processing plants, add oil of mirbane swelling 12h in the 250ml there-necked flask of 60ml; Speed with 1 ℃/2min is warming up to 80 ℃, adds the iron(ic) chloride of 7g under certain stirring velocity, and sustained reaction to resin residual chlorine content is 5%, obtains the polystyrene-divinylbenzene polymeric adsorbent; Take out most reaction mother liquor, with 600ml methylal and the above-mentioned polystyrene resin of methanol wash.The toluene swelling 12h that adds 60ml; The control solution temperature is 40 ℃, under the stirring velocity of 110rpm, constantly drip indoles 50ml sustained reaction 5h, take out and filter, with weight percent 4% hydrochloric acid drip washing, extracting, oven dry, products therefrom is the indyl modification complex function polymeric adsorbent, this resin indyl content is 0.5mmol/g, and micro pore volume is 0.93cm
3/ g, specific surface area is 1490m
2/ g.The resin structure unit is as follows:
Embodiment 6
Get the 30g degree of crosslinking and be 8% chlorine ball productions such as (, cl content is 18%) Langfang, Hebei electric power resin processing plants, add oil of mirbane swelling 18h in the 500ml there-necked flask of 150ml; Speed with 1 ℃/4min is warming up to 120 ℃, adds the tin chloride of 15g under certain stirring velocity, and sustained reaction to resin residual chlorine content is 4%, obtains the polystyrene-divinylbenzene polymeric adsorbent; Take out most reaction mother liquor, with 2L ethanol and washing with acetone polystyrene resin.The benzene swelling 8h that adds 150ml; The control solution temperature is 70 ℃, under the stirring velocity of 50rpm, constantly drip 3-chloro indoles 15ml sustained reaction 6h, take out and filter, with weight percent 4% hydrochloric acid drip washing, extracting, oven dry, products therefrom is a 3-chloro indyl modification complex function polymeric adsorbent, this resin 3-chloro indyl content is 0.03mmol/g, and micro pore volume is 0.98cm
3/ g, specific surface area is 1510m
2/ g.The resin structure unit is as follows:
Embodiment 7
Get the 30g degree of crosslinking and be 8% chlorine ball productions such as (, cl content is 18%) Langfang, Hebei electric power resin processing plants, add ethylene dichloride swelling 10h in the 500ml there-necked flask of 180ml; Speed with 1 ℃/6min is warming up to 40 ℃, adds the iron(ic) chloride of 9g under certain stirring velocity, and sustained reaction to resin residual chlorine content is 9%, obtains the polystyrene-divinylbenzene polymeric adsorbent; Take out most reaction mother liquor, with 500ml washing with acetone polystyrene resin.The ethylene dichloride swelling 10h that adds 120ml; The control solution temperature is 50 ℃, under the stirring velocity of 90rpm, constantly drip indoles-3-sulfonic acid 60ml sustained reaction 6h, take out and filter, with weight percent 4% hydrochloric acid drip washing, extracting, oven dry, products therefrom is indoles-3-sulfonic group modification complex function polymeric adsorbent, this resin indoles-3-sulfonic group content is 1.5mmol/g, and micro pore volume is 0.58cm
3/ g, specific surface area is 780m
2/ g.The resin structure unit is as follows:
Embodiment 8
Get the 30g degree of crosslinking and be 8% chlorine ball productions such as (, cl content is 18%) Langfang, Hebei electric power resin processing plants, add ethylene dichloride swelling 10h in the 500ml there-necked flask of 120ml; Speed with 1 ℃/6min is warming up to 40 ℃, adds the iron(ic) chloride of 9g under certain stirring velocity, and sustained reaction to resin residual chlorine content is 9%, obtains the polystyrene-divinylbenzene polymeric adsorbent; Take out most reaction mother liquor, with 500ml washing with acetone polystyrene resin.The ethylene dichloride swelling 10h that adds 120ml; The control solution temperature is 50 ℃, under the stirring velocity of 90rpm, constantly drip indole-2-carboxylic acid 50ml sustained reaction 6h, take out and filter, 4% hydrochloric acid drip washing, extracting, oven dry, products therefrom is the indole-2-carboxylic acid base modified composite function absorption resin, this resin indole-2-carboxylic acid base content is 1.9mmol/g, and micro pore volume is 0.45cm
3/ g, specific surface area is 720m
2/ g.The resin structure unit is as follows:
Embodiment 9
Get the 30g degree of crosslinking and be 8% chlorine ball productions such as (, cl content is 18%) Langfang, Hebei electric power resin processing plants, add ethylene dichloride swelling 10h in the 500ml there-necked flask of 120ml; Speed with 1 ℃/6min is warming up to 80 ℃, adds the iron(ic) chloride of 9g under certain stirring velocity, and sustained reaction to resin residual chlorine content is 4%, obtains the polystyrene-divinylbenzene polymeric adsorbent; Take out most reaction mother liquor, with 500ml washing with acetone polystyrene resin.The ethylene dichloride swelling 10h that adds 120ml; The control solution temperature is 50 ℃, under the stirring velocity of 90rpm, constantly drip indole-3-formaldehyde 60ml sustained reaction 6h, take out and filter, 4% hydrochloric acid drip washing, extracting, oven dry, products therefrom is the indole-3-formaldehyde base modified composite function absorption resin, this resin indole-3-formaldehyde base content is 0.02mmol/g, and micro pore volume is 0.78cm
3/ g, specific surface area is 1090m
2/ g.The resin structure unit is as follows:
Claims (7)
1. pyrryl modification complex function polymeric adsorbent is characterized in that its structural unit is as follows:
Wherein R is:
2. pyrryl modification complex function polymeric adsorbent according to claim 1 is characterized in that its specific surface area is 50-1600m
2/ g, micro pore volume are 0.01-1.0cm
3/ g, exchange capacity are 0.1-5.0mmol/g.
3. the preparation method of a pyrryl modification complex function polymeric adsorbent may further comprise the steps:
A) the chlorine ball is swollen in oil of mirbane, substituted-nitrobenzene, ethylene dichloride or the orthodichlorobenzene solvent, add zinc chloride or iron trichloride, tin tetrachloride as catalyzer, progressively be warming up to 20-120 ℃, control resin residual chlorine content is that 4-15% determines reaction end, obtains the polystyrene-divinylbenzene polymeric adsorbent;
B) steps A) after the reaction, take out most reaction mother liquor, residual solvent and the catalyzer of one or more organic solvent flush awaies in water or ethanol, acetone, methylal, the methyl alcohol; Make swelling agent with trichloroethane, oil of mirbane, substituted-nitrobenzene, ethylene dichloride, orthodichlorobenzene, benzene or toluene then, consumption is 2-6 a times of weight resin; Under 30-90 ℃ temperature, add functionalization pyrroles reagent, consumption is 0.5-3 a times of weight resin, further reacts with resin surfaces externally and internally residual chlorine methyl, can make the pyrryl modification complex function polymeric adsorbent.
4. the preparation method of a kind of pyrryl modification complex function polymeric adsorbent according to claim 3 is characterized in that steps A) in, the consumption of oil of mirbane, ethylene dichloride or orthodichlorobenzene is 2-6 a times of chlorine ball.
5. according to the preparation method of claim 3 or 4 described a kind of pyrryl modification complex function polymeric adsorbents, it is characterized in that steps A) in, the amount of catalyzer zinc chloride, iron trichloride or tin tetrachloride is the 4-50% of chlorine ball weight.
6. according to the preparation method of claim 3 or 4 described a kind of pyrryl modification complex function polymeric adsorbents, it is characterized in that step B) in, functionalization pyrroles's reagent of adding is pyrroles, N-methylpyrrole, N-N-ethyl pyrrole N-, indoles, 3-chloro indoles, indoles-3-sulfonic acid, indole-2-carboxylic acid or indole-3-formaldehyde.
7. according to the preparation method of claim 3 or 4 described a kind of pyrryl modification complex function polymeric adsorbents, it is characterized in that step B) in, the reaction times that adds functionalization pyrroles reagent is 2-24 hour.
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|---|---|---|---|---|
| CN103254333A (en) * | 2013-05-21 | 2013-08-21 | 南京工业大学 | Ultrahigh crosslinked resin SX-01 and application thereof |
| CN110885394A (en) * | 2019-12-17 | 2020-03-17 | 万华化学集团股份有限公司 | Triazine group modified macroporous resin and preparation method thereof |
| CN114082408A (en) * | 2021-10-22 | 2022-02-25 | 江苏海普功能材料有限公司 | Chelating ion exchange adsorbent and preparation and application thereof |
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| US20030144421A1 (en) * | 2002-01-25 | 2003-07-31 | Dixon Arthur R. | Surface graft modified resins and formation thereof |
| CN1858088A (en) * | 2006-04-25 | 2006-11-08 | 南京大学 | Pyridyl modified composite function super high crosslinked adsorptive resin and its preparing method |
| CN1865302A (en) * | 2006-04-25 | 2006-11-22 | 南京大学 | Composite functional super high cross-linked adsorption resin containing quaternary amine group, and its preparation method |
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Patent Citations (4)
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|---|---|---|---|---|
| CN1346708A (en) * | 2001-11-05 | 2002-05-01 | 南京大学环境学院 | Process for synthesizing weakly alkaline anionic exchange resin with double functions and superhigh cross-linking |
| US20030144421A1 (en) * | 2002-01-25 | 2003-07-31 | Dixon Arthur R. | Surface graft modified resins and formation thereof |
| CN1858088A (en) * | 2006-04-25 | 2006-11-08 | 南京大学 | Pyridyl modified composite function super high crosslinked adsorptive resin and its preparing method |
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Cited By (5)
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| CN103254333A (en) * | 2013-05-21 | 2013-08-21 | 南京工业大学 | Ultrahigh crosslinked resin SX-01 and application thereof |
| CN110885394A (en) * | 2019-12-17 | 2020-03-17 | 万华化学集团股份有限公司 | Triazine group modified macroporous resin and preparation method thereof |
| CN110885394B (en) * | 2019-12-17 | 2022-03-11 | 万华化学集团股份有限公司 | Triazine group modified macroporous resin and preparation method thereof |
| CN114082408A (en) * | 2021-10-22 | 2022-02-25 | 江苏海普功能材料有限公司 | Chelating ion exchange adsorbent and preparation and application thereof |
| CN114082408B (en) * | 2021-10-22 | 2024-01-02 | 江苏海普功能材料有限公司 | Chelating ion exchange adsorbent and preparation and application thereof |
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